Redox-Responsive Hydrogen-Bonding Systems for Supramolecular Applications

受DNA的标志性例子的启发，DNA是由两股天然聚合物组成的，它们通过弱力结合在一起，可以在需要时分离，圣地亚哥州立大学的史密斯教授探索了控制合成聚合物链可逆组装和分离的新方法。这种聚合物材料提供了缺陷纠正和刺激响应特性的潜力。除了在响应材料，超分子聚合物和开关方面的潜在重大影响外，该研究项目还为不同群体的本科生和研究生提供了良好的教育和培训机会，其中许多人来自科学界代表性不足的群体。这个研究项目鼓励学生在分子水平上破译正在发生的事情，从而提高他们的化学推理和解决问题的能力。这些能力在他们未来的职业生涯中很有价值。该项目的总体目标是开发具有氧化还原活性的线性氢键二聚体，使其结合强度可以被电化学还原/氧化强烈但可逆地干扰。这个研究项目分为三个具体目标。目的1是通过比较两种系统的伏安行为来确定两个电子和一个质子（H+）和一个电子转移对强烈扰动氢键的意义。目标2是开发新的氧化还原活性氢键二聚体，其中质子在氢键上的转移被有意地用来放大电子转移的效果，从而使结合强度大大增加或减少。最后，在Aim 3中，研究小组探索了使用氧化还原活性阵列来创建氧化还原响应的超分子聚合物系统。

Inspired by the iconic example of DNA, which is composed of two strands of natural polymers that are held together by weak forces and can be separated when desired, Professor Smith of San Diego State University explores novel approaches to controlling the reversible assembly and separation of synthetic polymer strands. Such polymeric materials offer the potential for correction of defects and stimuli-responsive properties. In addition to the potential for significant impact in responsive materials, supramolecular polymers and switches, this research program provides excellent education and training opportunities to a diverse group of undergraduate and graduate students, many of whom are from groups under-represented in science. This research project encourages students to decipher what is happening at the molecular level - sharpening their chemical reasoning and problem solving abilities. These abilities are valuable in their future careers. The overall goal of this project is to develop the chemistry of redox-active, linear hydrogen-bond dimers such that binding strength can be strongly, but reversibly, perturbed by electrochemical reduction/oxidation. This research program is broken into three specific aims. Aim 1 is to establish the significance of two electrons and one proton (H+) verse one electron transfer for strongly perturbing hydrogen bonding by comparing the voltammetric behavior of these two types of systems. Aim 2 is to develop new redox-active hydrogen bond dimers in which proton transfer across a hydrogen bond is purposely used to amplify the effect of electron transfer in such a way that binding strength is either greatly increased or decreased. Finally, in Aim 3, the research team explores the use of the redox-active arrays developed to create redox-responsive, supramolecular, polymeric systems.